1. Field of the Invention
The subject invention relates to novel copolymers which contain a UVA light-absorbing monomer and/or a UVB light-absorbing monomer; and a hydrophilic monomer component. The copolymers may optionally contain a hydrophobic monomer component. The copolyesters may be used in fabric care, skin care, and in other applications recognized by those skilled in the art.
2. Prior Art
The harmful effects of solar radiation are well known. The UVB (290-320 nm) portion of the solar spectrum is largely responsible for erythema (sunburn) and cancer (M. M. Rieger, Cosmet Toiletries, 102(3):91 (1987); C. Taylor, Skin Cancer Foundation J., 4:90 (1986)). The UVA (320-400 nm) portion of the solar spectrum is believed to be responsible for skin aging and premature wrinkling (L. H. Kligman, F. J. Akin, and A. M. Kligman, J. Invest. Dermatol., 84:272 (1985)).
In addition, UV light is also known to fade garments, especially in areas of high solar intensity This problem has been partially addressed via the application of various monomeric chromophores to garment surfaces (K. H. Remley U.S. Pat. No. 4,153,744; R. J. Bernhardt et al U.S. Pat. No. 4,788,054; P. C. Crews, et al., Text. Chem. Color, 11:21 (1987); B. Milligan et al., Polym. Deorad. Stab., 10(4):335 (1985)).
None of the above references relating to the protection of garments from solar radiation teach the use of polymeric UV light-absorbers.
Several references teach polymeric UV light-absorbers which selectively filter out either UVB or UVA light at maximum absorbance (.lambda.max). None of these references, however, teach the use of either a hydrophobic or hydrophilic component to control the dispersibility and adsorption properties of the polymer. Further, with regard to the embodiment of the invention relating to copolymers with both UVA and UVB monomers (i.e., broad spectrum absorbency), none of these references teach copolymers with such broad spectrum absorbency.
Ciaudelli U.S. Pat. No. 3,864,473 teaches the use of 4-dimethylaminobenzoate-grafted poly(ethyleneimine) as a polymeric UV light absorber. The use of the aminobenzoate chromophore alone, however, limits the polymer's maximum absorbance to the UVB range. Moreover, the use of either a hydrophobic or hydrophilic component to control the dispersibility and adsorption properties of the polymer is not taught.
Cho et al. U.S. Pat. No. 4,524,061 teaches the use of poly(methacrylate) poly(vinylpyrrolidone) poly(vinyl 4-aminobenzoate) copolymer as a polymeric UV light absorber. The use of the aminobenzoate chromophore alone, however, limits the polymer's maximum absorbance to the UVB range. Moreover, the use of either a hydrophobic or hydrophilic component to control the dispersibility and adsorption properties of the polymer is not taught.
French Patent 2,617,399 to Lapoiriere et al. teaches the use of cinnamate-grafted poly(acrylamide) as a polymeric UV light absorber. The use of the cinnamate chromophore alone, however, limits the polymer's maximum absorbance to the UVB range. Moreover, the use of either a hydrophobic or hydrophilic component to control the dispersibility and adsorption properties of the polymer is not taught.
Hill U.S. Pat. No. 4,545,980 teaches the use cinnamate-grafted poly(dimethylsiloxanol) as a polymeric UV light absorber. The use of the cinnamate chromophore alone, however, limits the polymer's maximum absorbance to the UVB range. Moreover, the use of either a hydrophobic or hydrophilic component to control the dispersibility and adsorption properties of the polymer is not taught.
Japanese Patent 60,099,186 to Pola Chemical Industries, Ltd. teaches the use of poly(glycidol)/poly(4-glycidylaminobenzoate) copolymer as a polymeric UV light absorber. The use of the aminobenzoate chromophore alone, however, limits the polymer's maximum absorbance to the UVB range. Moreover, the use of either a hydrophobic or hydrophilic component to control the dispersibility and adsorption properties of the polymer is not taught.
B. Jacquet et al., Rev. Gen. Caoutch. Plast., 54(575):85 (1977) teach the use of poly(vinyl stearate)/poly(vinyl (4'-dimethylaminobenzoyloxy)acetate) copolymer as a polymeric UV light absorber. The use of the aminobenzoate chromophore alone, however, limits the polymer's maximum absorbance to the UVB range. Moreover, the use of either a hydrophobic or hydrophilic component to control the dispersibility and adsorption properties of the polymer is not taught.
German Patent 2,726,568 to Jacquet et al., teaches the use of cyanodiphenylacrylic acid-grafted poly(vinyl acetate) as a polymeric UV light absorber. The use of the cyanodiphenylacrylate chromophore alone, however, limits the polymer's maximum absorbance to the UVB range. Moreover, the use of either a hydrophobic or hydrophilic component to control the dispersibility and adsorption properties of the polymer is not taught.
Forestier et al. U.S. Pat. No. 4,839,160 teaches the use of benzylidenecamphor-grafted poly(acrylamide) as a polymeric sunscreen. The use of the benzylidenecamphor chromophore alone, however, limits the polymer's maximum absorbance to the UVA range. Moreover, the use of either a hydrophobic or hydrophilic component to control the dispersibility and adsorption properties of the polymer is not taught.
In the applicant's co-pending application filed Apr. 23, 1992 and titled "Water Dispersible Copolymer Containing UVA and UVB Light-Absorbing Monomers", there is taught a novel water-dispersible polymeric sunscreen based on repeating units of a UVA light-absorbing monomer, a UVB light-absorbing monomer, and a poly(alkylene glycol) such as poly(ethylene glycol) as a hydrophilic group. The addition of poly(ethylene glycol) was found to be necessary for dispersion of the polymer through an aqueous medium. However, due to its relatively high molecular weight, the poly(ethylene glycol) unit lowers the overall weight percent of the UVA and UVB light-absorbing moieties, thereby dramatically diluting their efficiency. That is, the weight percent of UVA and UVB light absorbing moiety in the water dispersible polymer when utilizing poly(ethyleneglycol) is limited to about 50% if one also wishes to maintain water dispersibility. By contrast, if the hydrophilic moiety is of substantially lower molecular weight, such as in the polymers of the subject invention, a UVA and/or UVB chromophore loading of up to 95%, and perhaps higher, may be achieved while still maintaining water dispersibility.
In addition, several references teach that hydroxyamino acids and diamino acids may be copolymerized with difunctional monomers to give polyamides and polyurethanes However, none of the references teach the copolymerization of lysine (or other low molecular weight hydrophilic group of the invention) with a UVA and/or UVB light-absorbing chromophore.
Y. Ihara et al., J. Polym. Sci., Part A-1, 9(8):2413 (1971) teach the copolymerization of lysine with terephthaloyl chloride, with 4,4'-diphenyldicarbonyl dichloride, and with 2,6-naphthalenedicarbonyl dichloride to give optically active polyamides useful for amino acid adsorption studies. The copolymerization of lysine, or other hydrophilic groups of the invention, with a UVA and/or UVB light-absorbing chromophore is neither taught nor suggested.
Lim et al. U.S. Pat. No. 4,324,684, teaches the copolymerization of lysine with terephthaloyl chloride to afford a polyamide membrane for encapsulating hemoglobin. The copolymerization of lysine, or other hydrophilic groups of the subject invention, with a UVA and/or UVB light-absorbing chromophore is neither taught nor suggested.
Marinovic U.S. Pat. No. 4,743,632 teaches the copolymerization of poly(butylene glycol), dicyclohexylmethane-4,4'-diisocyanate, and lysine, serine, or arginine to give polyetherurethanes useful as surgical adhesive sealants. The copolymerization of lysine, or other hydrophilic groups of the invention, with a UVA and/or UVB light-absorbing chromophore is neither taught nor suggested.
In each of the above-identified references, the polymers used differ from the copolymers of the subject invention, there is no teaching of the use of both a UVA and a UVB light-absorbing unit in conjunction with a low molecular weight (i.e., monomeric) hydrophilic unit to control dispersion properties, and there is no teaching of the use of a UVA light-absorbing unit, a UVB light-absorbing unit, a low molecular weight (i.e.,, monomeric) hydrophilic unit, and optionally a hydrophobic unit to control adsorbance capabilities of the resulting polymer.
Thus, there is a need in the art for novel copolymers comprising a UVB light-absorbing moiety and/or a UVA light-absorbing moiety, a low molecular weight (i.e., monomeric) hydrophilic moiety which allows for a high weight percentage of UVA and/or UVB moiety (i.e., loading of up to 95%) in the resulting polymer and further allows the polymer to be solvated in aqueous media, and optionally a hydrophobic moiety to fine-tune the polymer's ability to adhere to a desired surface.